Piezoelectric material, piezoelectric element, liquid ejecting head, liquid ejecting apparatus, ultrasonic sensor, piezoelectric motor, and power generator

ABSTRACT

A piezoelectric material contains a first component that is a rhombohedral crystal that is configured to have a complex oxide with a perovskite structure and Curie temperature Tc1 and a second component that is a crystal other than a rhombohedral crystal that is configured to have a complex oxide with the perovskite structure and Curie temperature Tc2, in which |Tc1−Tc2| is equal to or less than 50° C.

BACKGROUND

1. Technical Field

The present invention relates to a piezoelectric material used inpiezoelectric elements, or the like mounted in various devices such asactuators, ultrasonic devices such as ultrasonic oscillators, ultrasonicmotors, pressure sensors, and pyroelectric elements such as IR sensors,a piezoelectric element using the material, a liquid ejecting head, aliquid ejecting apparatus, an ultrasonic sensor, a piezoelectric motor,and a power generator.

2. Related Art

A piezoelectric material, which is used as a piezoelectric layer(piezoelectric ceramics) constituting a piezoelectric element, or thelike mounted in various devices such as actuators, ultrasonic devicessuch as ultrasonic oscillators, ultrasonic motors, pressure sensors, andpyroelectric elements such as IR sensors is required to have aremarkable piezoelectric characteristic, and as a representative examplethereof, lead zirconate titanate (PZT) is exemplified.

However, from an environmental sensitivity point of view, apiezoelectric material whose lead content is suppressed is desired. Assuch a lead-free piezoelectric material, there are a piezoelectricmaterial that includes an alkali metal such as K_(x)Na_((1-x))NbO₃, and(Ba, Na)TiO₃, a piezoelectric material such as BiFeO₃—BaTiO₃, and thelike.

With regard to such a piezoelectric material, it is known that aremarkable piezoelectric characteristic can be obtained by using acomposition near a Morphotropic Phase Boundary (MPB). However, in aphase diagram that employs compositions for the horizontal axis andtemperatures for the vertical axis, the MPB line of PZT is substantiallyparallel to the temperature axis or positioned vertical to thecomposition axis, but an MPB line of a lead-free piezoelectric materialis generally inclined with respect to the temperature axis (for example,refer to FIG. 1 of JP-A-2009-215111, or the like). When the MPB line isinclined as described above, even if a composition positioned on the MPBline at a specific temperature, for example, room temperature accordingto a desired characteristic is selected, it is set away from the MPBline on the composition-temperature state diagram when the environmentaltemperature changes, and thus, there is a problem in that there is atemperature area in which a piezoelectric characteristic, and dielectriccharacteristic of an element deteriorates due to changes inenvironmental temperature, generation of heat during usage, or the like.

Thus, from a desire that the MPB line is erect if possible in the phasediagram described above and a desire that a piezoelectric material has aremarkable piezoelectric characteristic and dielectric characteristic ataround a normal temperature (room temperature) and can be used even at atemperature as high as possible, a piezoelectric material that has Curietemperature (Tc) as high as it can be, which is generally inverselyproportional to the piezoelectric characteristic, has been demanded.

For this reason, technologies for improving temperature dependency bylaminating a plurality of piezoelectric materials having differentcompositions have been proposed (refer to JP-A-2003-277143 andJPA-2011-181764), but the fact that the plurality of differentpiezoelectric materials should be used is a problem.

As described above, currently, there is no lead-free piezoelectricmaterial compared to PZT, and thus, introduction of a lead-freepiezoelectric material having a remarkable piezoelectric characteristicand dielectric characteristic in a wide use environment temperaturerange and having a high Curie temperature has been greatly desired.

Note that such a problem also arises not only in ink jet-type recordingheads but also in other liquid ejecting heads that discharge dropletsother than ink, and also arises even in piezoelectric elements used indevices other than such liquid ejecting heads.

SUMMARY

An advantage of some aspects of the invention is to provide apiezoelectric material that reduces the burden on the environment, andhas a remarkable piezoelectric characteristic and dielectriccharacteristic in a wide use environment temperature range and has ahigh Curie temperature, a piezoelectric element using the material, aliquid ejecting head, a liquid ejecting apparatus, an ultrasonic sensor,a piezoelectric motor, and a power generator.

According to an aspect of the invention, there is provided apiezoelectric material containing a first component that is arhombohedral crystal in a single composition and that is configured tohave a complex oxide with a perovskite structure and Curie temperatureis set to be Tc1 and a second component that is a crystal other than arhombohedral crystal in a single composition and that is configured tohave a complex oxide with the perovskite structure and Curie temperatureis set to be Tc2, and in which the absolute value of the differencebetween Tc1 and Tc2|Tc1−Tc2| is equal to or lower than 50° C.

In this case, since the piezoelectric material does not contain lead, anenvironmental burden can be reduced, and the piezoelectric material thathas a remarkable piezoelectric characteristic and dielectriccharacteristic in a wide use environment temperature range and has ahigh Curie temperature is produced.

Here, it is preferable that a composition near an MPB line be providedin a phase diagram that employs a composition ratio of a first componentand a second component for the horizontal axis and temperature for thevertical axis. In this case, by selecting each component, thepiezoelectric material that has a remarkable piezoelectriccharacteristic and dielectric characteristic in a use environmenttemperature range and has a high Curie temperature can be realized, in awide composition range.

In addition, it is preferable that the relationship of|Tc1−Tc2|/|Tc1+Tc2|≦0.1 be satisfied. Accordingly, by further limitingthe range of the absolute value of the difference between Tc1 andTc2|Tc1−Tc2|, the piezoelectric material that has a remarkablepiezoelectric characteristic and dielectric characteristic in a wide useenvironment temperature range and has a high Curie temperature canrealized more reliably.

In addition, it is preferable that Curie temperature be equal to orhigher than 280° C. In this case, the piezoelectric material that can beused in a wide use environment temperature range can be realized.

In addition, it is preferable that the molar ratio of the firstcomponent to (the first component+the second component) be equal to orhigher than 0.1 and equal to or lower than 0.9. In this case, by thuslyselecting each component, the piezoelectric material that has aremarkable piezoelectric characteristic and dielectric characteristic ina wide use environment temperature range and has a high Curietemperature can be realized in a wide composition range.

In addition, it is preferable that the first component be (Bi, Na,La)TiO₃, and the second component be NaNbO₃. In this case, apiezoelectric material that has a remarkable piezoelectriccharacteristic and dielectric characteristic in a wide use environmenttemperature range and has a high Curie temperature can be realized morereliably.

In addition, it is preferable that the first component be (Bi, Na,La)TiO₃, and the second component be (K, Na)NbO₃ to which at least onekind selected from Li and Ta is added. In this case, a piezoelectricmaterial that has a remarkable piezoelectric characteristic anddielectric characteristic in a wide use environment temperature rangeand has a high Curie temperature can be realized more reliably.

In addition, it is preferable that the first component be (Bi, Na,La)TiO₃, and the second component be (Bi, K)TiO₃. In this case, apiezoelectric material that has a remarkable piezoelectriccharacteristic and dielectric characteristic in a wide use environmenttemperature range and has a high Curie temperature can be realized morereliably.

In addition, it is preferable that the first component be (Bi, Na,Ba)TiO₃, (Bi, Na)TiO₃, and one kind selected from (Bi, Na)TiO₃, (Bi, La)(Sc, Ti)O₃, and (Bi, La) (Zn, Ti)O₃ to which Ca is added, and the secondcomponent be NaNbO₃ to which at least one kind selected from Li and Tais added. In this case, a piezoelectric material that has a remarkablepiezoelectric characteristic and dielectric characteristic in a wide useenvironment temperature range and has a high Curie temperature can berealized more reliably.

According to another aspect of the invention, there is provided apiezoelectric element which includes a piezoelectric layer configured tohave the piezoelectric material according to the aspect described aboveand an electrode provided on the piezoelectric layer.

In this case, since the piezoelectric element does not contain lead, anenvironmental burden can be reduced, and the piezoelectric material thatcan maintain excellent characteristics in a wide use environmenttemperature range can be realized.

In addition, according to still another aspect of the invention, thereis provided a liquid ejecting head that includes a pressure generatingchamber that communicates with a nozzle opening and a piezoelectricelement that has a piezoelectric layer and an electrode provided on thepiezoelectric layer, and the piezoelectric layer is formed of thepiezoelectric material according to the above-described aspect.

In this case, since the piezoelectric element does not contain lead, anenvironmental burden can be reduced, and the liquid ejecting head thatincludes a piezoelectric element that can maintain excellentcharacteristics in a wide use environment temperature range can berealized.

In addition, according to still another aspect of the invention, thereis provided a liquid ejecting apparatus that includes the liquidejecting head according to the above-described aspect.

In this case, since the piezoelectric element does not contain lead, anenvironmental burden can be reduced, and the liquid ejecting apparatusequipped with a liquid ejecting head that includes a piezoelectricelement that can maintain excellent characteristics in a wide useenvironment temperature range can be realized.

In addition, according to still another aspect of the invention, thereis provided an ultrasonic sensor that includes a vibrating unit thattransmits a displacement to the outside which is caused due to drivingof the piezoelectric element according to the above-described aspect anda matching layer that transmits a generated pressure wave to theoutside.

In this case, since the piezoelectric element does not contain lead, anenvironmental burden can be reduced, and the ultrasonic sensor equippedwith a piezoelectric element that can maintain excellent characteristicsin a wide use environment temperature range can be realized.

In addition, according to still another aspect of the invention, thereis provided a piezoelectric motor that includes at least a vibrator inwhich the piezoelectric element according to the above-described aspectis arranged, and a moving body contacting the vibrator.

In this case, since the piezoelectric element does not contain lead, anenvironmental burden can be reduced, and the piezoelectric motorequipped with a piezoelectric element that can maintain excellentcharacteristics in a wide use environment temperature range can berealized.

In addition, according to still another aspect of the invention, thereis provided a power generator that includes an electrode for taking outa charge generated by the piezoelectric element according to theabove-described aspect from the electrode.

In this case, since the piezoelectric element does not contain lead, anenvironmental burden can be reduced, and the power generator equippedwith a piezoelectric element that can maintain excellent characteristicsin a wide use environment temperature range can be realized.

BRIEF DESCRIPTION OF THE DRAWINGS

Embodiments of the invention will be described with reference to theaccompanying drawings, wherein like numbers reference like elements.

FIG. 1 is a graph plotting an example of a phase diagram for describinga piezoelectric material according to an aspect of the invention.

FIG. 2 is a graph plotting an example of a phase diagram for describingthe piezoelectric material according to the aspect of the invention.

FIG. 3 is a graph plotting an example of a phase diagram for describingthe piezoelectric material according to the aspect of the invention.

FIG. 4 is an exploded perspective view illustrating a schematicconfiguration of a recording head according to a first embodiment of theinvention.

FIG. 5 is a plan view of the recording head according to the firstembodiment of the invention.

FIG. 6 is a cross-sectional view of the recording head according to thefirst embodiment of the invention.

FIG. 7 is a diagram illustrating a schematic configuration of arecording apparatus according to an embodiment of the invention.

DESCRIPTION OF EXEMPLARY EMBODIMENTS

Hereinafter, the invention will be described in detail based onembodiments.

Piezoelectric Material

A piezoelectric material contains a first component that is arhombohedral crystal in a single composition and that is configured tohave a complex oxide with a perovskite structure and Curie temperatureis set to be Tc1 and a second component that is a crystal other than therhombohedral crystal in a single composition and that is configured tohave a complex oxide with the perovskite structure and Curie temperatureis set to be Tc2, and the absolute value of the difference between Tc1and Tc2|Tc1−Tc2| is equal to or lower than 50° C.

With the piezoelectric material which is obtained by forming a solidsolution of the first component and the second component which satisfythe above condition, an MPB line can be made substantially verticallyerect in a phase diagram that employs a composition ratio of the firstcomponent and the second component for the horizontal axis andtemperature for the vertical axis.

Here, the first component is the rhombohedral crystal and is a complexoxide with the perovskite structure and has a relatively high Curietemperature, and for example, (Bi, Na, La)TiO₃, (Bi, Na, Ba)TiO₃, (Bi,Na)TiO₃, and (Bi, Na, Ba)TiO₃ to which Ca is added, (Bi, La) (St, Ti)O₃,and (Bi, Na)(Sc, Ti)O₃, Bi(FeMn)O₃, and the like can be exemplified.

The second component is a crystal other than the rhombohedral crystal,in other words, a tetragonal crystal or an orthorhombic crystal, and hasa relatively high Curie temperature, and NaNbO₃, (K, Na)NbO₃, (Bi,K)TiO₃, and NaTaO₃ to which at least one kind selected from Li and Ta isadded, and the like can be exemplified.

Here in a phase diagram that employs a composition ratio of the firstcomponent and the second component for the horizontal axis andtemperature for the vertical axis, a line connecting Tc1 of the firstcomponent that is the rhombohedral crystal and Tc2 of the secondcomponent of a crystal other than the rhombohedral crystal, for example,a tetragonal crystal is positioned substantially in parallel to the axisof the composition ratio. This is because the composition is of a solidsolution of the first component and the second component of which theabsolute value of the difference between Tc1 and Tc2|Tc1−Tc2| is equalto or lower than 50° C.

Thus, by using the composition along the MPB line, a piezoelectricmaterial of which Curie temperature of the composition is equal to orhigher than 280° C. and which can maintain almost constantcharacteristics even when temperature of a use environment changes canbe realized.

As described above, the composition of the piezoelectric material is acomposition in which the first component and the second component formsa solid solution as described above, a composition near the MPB line inthe phase diagram that employs a composition ratio of the firstcomponent and the second component for the horizontal axis andtemperature for the vertical axis, and Curie temperature of thecomposition Tc3 is preferably equal to or higher than 280° C.

Here, the MPB line is a boundary for creating different crystal systems,a crystal system has composition dependency, and a dielectric constant,a piezoelectric constant, and a Young's modulus have compositiondependency. Thus, in a composition that forms the MPB line, a dielectricconstant and a piezoelectric constant have a maximum value, and aYoung's modulus has a minimum value. A composition region is defined fora dielectric constant and a piezoelectric constant in which thecharacteristics are exhibited within the range of 70% or more of a peakvalue (a value on the MPB), and a composition region for a Young'smodulus in which the characteristic is within the range of 130% of theminimum value as compositions near MPB.

Here, the relationship of |Tc1−Tc2|/|Tc1+Tc2|≦0.1 is preferablysatisfied. With the relationship, the absolute value of the differencebetween Tc1 and Tc2|Tc1−Tc2| is within a predetermined range, andpreferably, Curie temperature of the composition Tc3 is assuredly equalto or higher than 280° C.

Here, it is preferable that the molar ratio of the first component to(the first component+the second component) be equal to or higher than0.1 and equal to or lower than 0.9. By appropriately selecting the firstcomponent and the second component, a piezoelectric material that has ahigh Curie temperature Tc3, or preferably 280° C. or higher in a widecomposition range and can maintain characteristics almost constant evenwhen temperature of a use environment changes can be realized.

Examples of each of the first component and the second component whichcan be applied to the piezoelectric material of the invention are shownbelow.

For example, the first component is (Bi, Na, La)TiO₃ and the secondcomponent is NaNbO₃.

In addition, the first component is (Bi, Na, La)TiO₃ and the secondcomponent is (K, Na)NbO₃ to which at least one kind selected from Li andTa is added.

In addition, the first component is (Bi, Na, La)TiO₃ and the secondcomponent is (Bi, K)TiO₃.

In addition, the first component is (Bi, Na, Ba)TiO₃, (Bi, Na)TiO₃, andone kind selected from (Bi, Na, Ba)TiO₃ to which Ca is added, (Bi, La)(St, Ti)O₃, and (Bi, Na)(Sc, Ti)O₃, and the second component is (K,Na)NbO₃ to which at least one kind selected from Li and Ta is added.

Hereinbelow, description will be provided in more detail with specificexamples.

FIG. 1 illustrates a phase diagram that employs a composition ratio of afirst component and a second component for the horizontal axis andtemperature for the vertical axis when the first component is (Bi, Na,La)TiO₃ and the second component is NaNbO₃. In this case, Curietemperature Tc of (Bi, Na, La)TiO₃ that is the first component is 335°C., Curie temperature of NaNbO₃ that is the second component is 365° C.,the MPB line M1 is substantially vertically erect, and a compositionratio of (Bi, Na, La)TiO₃ merely changes in the range of 0.6 to 0.5. Inaddition, Curie temperature Tc3 at the peak of the MPB line M1 is 330°C. Accordingly, a piezoelectric material that has a remarkablepiezoelectric characteristic and dielectric characteristic in a wide useenvironment temperature range and has a high Curie temperature can berealized.

FIG. 2 illustrates a phase diagram that employs a composition ratio of afirst component and a second component for the horizontal axis andtemperature for the vertical axis when the first component is (Bi, Na,La)TiO₃ and the second component is (K,Na)NbO3 to which at least one ofLi and Ta is added. In this case, Curie temperature Tc of (Bi, Na,La)TiO₃ that is the first component is 335° C., Curie temperature Tc thesecond component is 325° C., the MPB line M2 is substantially verticallyerect, a composition ratio of (Bi, Na, La)TiO₃ merely changes in therange of 0.46 to 0.63. In addition, Curie temperature Tc3 at the peak ofthe MPB line M2 is 330° C. Accordingly, a piezoelectric material thathas a remarkable piezoelectric characteristic and dielectriccharacteristic in a wide use environment temperature range and has ahigh Curie temperature can be realized.

FIG. 3 illustrates a phase diagram that employs a composition ratio of afirst component and a second component for the horizontal axis andtemperature for the vertical axis when the first component is (Bi, Na,La)TiO₃ and the second component is (Bi, K)TiO₃. In this case, Curietemperature Tc of (Bi, Na, La)TiO₃ that is the first component is 335°C., Curie temperature Tc of (Bi, K)TiO₃ that is the second component is380° C., the MPB line M3 is substantially vertically erect, and acomposition ratio of (Bi, Na, La)TiO₃ merely changes in the range of0.35 to 0.31. In addition, Curie temperature Tc3 at the peak of the MPBline M3 is 347° C. Accordingly, a piezoelectric material that has aremarkable piezoelectric characteristic and dielectric characteristic ina wide use environment temperature range and has a high Curietemperature can be realized.

Although not shown in the drawings, even when the first component is(Bi, Na, Ba)TiO₃, (Bi, Na)TiO₃, and one kind selected from (Bi, Na,Ba)TiO₃ to which Ca is added, (Bi, La) (St, Ti)O₃, and (Bi, Na) (Sc,Ti)O₃, and the second component is (K, Na) NbO₃ to which at least onekind selected from Li and Ta is added, a phase diagram similar to FIGS.1 to 3 is obtained, the MPB line is substantially vertically erect, anda piezoelectric material that has a remarkable piezoelectriccharacteristic and dielectric characteristic in a wide use environmenttemperature range and has a high Curie temperature can be realized.Here, in FIGS. 1 to 3, the phase diagram includes a composition range(denoted by R in the drawing) formed as a rhombohedral crystal, acomposition range formed as a tetragonal crystal (denoted by T in thedrawing) or an orthorhombic crystal (denoted by O in the drawing), and acomposition range formed as a cubical crystal (denoted by C in thedrawing).

When the piezoelectric element is used as an actuator, the range of thepiezoelectric characteristics d33 is preferably 100 to 300 pC/N, andmore preferably 150 to 300 pC/N. In this case, the range of a Young'smodulus is preferably 30 to 80 GPa, and the range of Curie temperatureTc is preferably 70 to 350° C. and more preferably 100 to 300° C. Inaddition, the range of relative permittivity is preferably equal to orless than 2000 and more preferably 100 to 1000.

In addition, when the piezoelectric element is used as a sensor, therange of an e constant is preferably 3 to 15 C/m² and more preferably 5to 15 C/m². In addition, in this case, the range of a Young's modulus ispreferably 70 to 150 GPa and more preferably 80 to 130 GPa. In addition,the range of Curie temperature Tc is preferably 100 to 350° C. and morepreferably 120 to 300° C. In addition, the range of relativepermittivity is preferably equal to or less than 2000 and morepreferably 100 to 800.

Piezoelectric Element and Liquid Ejecting Head

FIG. 4 is an exploded perspective view illustrating a schematicconfiguration of an ink jet type recording head that is an example of aliquid ejecting head equipped with the piezoelectric element accordingto an embodiment of the invention. FIG. 5 is a plan view of FIG. 4, andFIG. 6 is a cross-sectional view taken by cutting along the line VI-VIof FIG. 5. As illustrated in FIGS. 4 to 6, a flow path forming substrate10 of the present embodiment is constituted by a silicon monocrystalsubstrate, and an elastic film 50 configured to have silicon dioxide isformed on one face of the substrate.

A plurality of pressure generating chambers 12 are provided in parallelin the flow path forming substrate 10 in the width direction of thesubstrate. In addition, a communication unit 13 is formed in an outerregion of the pressure generating chambers 12 in the longitudinaldirection of the flow path forming substrate 10, and the communicationunit 13 and each of the pressure generating chambers 12 communicate witheach other via ink supply paths 14 and communication paths 15 providedfor each of the pressure generating chambers 12. The communication unit13 constitutes a part of a manifold that serves as an ink chamber sharedby the pressure generating chambers 12 by communicating with a manifoldunit 31 of a protection substrate to be described later. The ink supplypaths 14 are formed having widths narrower than the pressure generatingchambers 12, and keeps resistance of ink flowing from the communicationunit 13 to the pressure generating chambers 12 against the flow pathconstant. Note that, in the present embodiment, the ink supply paths 14are formed by narrowing the width of the flow path from a single side,but the ink supply paths may be formed by narrowing the width of theflow path from both sides. In addition, the ink supply paths may beformed not by narrowing the width of the flow path but by narrowing thewidth in the thickness direction thereof. In the present embodiment, aliquid flow path constituted by the pressure generating chambers 12, thecommunication unit 13, the ink supply paths 14, and the communicationpaths 15 is provided in the flow path forming substrate 10.

In addition, a nozzle plate 20 in which nozzle openings 21, whichcommunicate with the pressure generating chambers 12 near the edge onthe opposite side of the ink supply paths 14, are drilled is fixed tothe flow path forming substrate 10 on the opening face side using anadhesive, a thermal welding film, or the like. Note that the nozzleplate 20 is formed of, for example, glass ceramics, silicon monocrystalsubstrate, stainless steel, or the like.

On the other hand, on the opposite side of the opening face of the flowpath forming substrate 10, the elastic film 50 described above isformed, and an adhesive layer 56 that is formed of titanium oxide forimproving adhesiveness to a base of first electrodes 60 such as theelastic film 50 is provided on the elastic film 50. Note that aninsulating film formed of zirconium oxide may be formed between theelastic film 50 and the adhesive layer 56 if necessary.

Further, the first electrodes 60, a piezoelectric layer 70 which is athin film having a thickness being equal to or thinner than 2 μm, orpreferably 0.3 to 1.5 μm, and second electrodes 80 are formed on theadhesive layer 56 in a laminating manner, configuring piezoelectricelements 300. Here, the piezoelectric element 300 refers to a portionincluding the first electrodes 60, the piezoelectric layer 70, and thesecond electrodes 80. Generally, one electrode of the electrodes of thepiezoelectric elements 300 is set to be a shared electrode, and theother electrode and the piezoelectric layer 70 are patterned for each ofthe pressure generating chambers 12. In the present embodiment, each ofthe first electrodes 60 is set to be a shared electrode of thepiezoelectric elements 300, and each of the second electrodes 80 is setto be an independent electrode of the piezoelectric elements 300, but itdoes not matter to reverse the setting according to a state of a drivecircuit or a wiring. In addition, here, the piezoelectric elements 300and a diaphragm of which displacement is caused due to driving of thepiezoelectric elements 300 are referred to as actuator devices. Notethat, in the example described above, the elastic film 50, the adhesivelayer 56, the first electrodes 60, and an insulating film provided ifnecessary act as a diaphragm, but it is of course not limited thereto,and for example, the elastic film 50 or the adhesive layer 56 may not beprovided. In addition, the piezoelectric elements 300 may also serve asa substantial diaphragm by itself.

In the present embodiment, the piezoelectric layer 70 is formed of thepiezoelectric material described above. Since the piezoelectric materialhas a remarkable piezoelectric characteristic and dielectriccharacteristic in a wide use environment temperature range and has highCurie temperature, a piezoelectric element that exhibits an excellentdisplacement characteristic in a wide use environment temperature rangecan be realized. In addition, since the piezoelectric material does notcontain lead, an environmental burden can be reduced.

Each of the second electrodes 80 that is an independent electrode of thepiezoelectric elements 300 is drawn out from a periphery of an end ofthe ink supply path 14, and is connected to each of leading electrodes90 that is formed of, for example, gold (Au), or the like, extendingonto the adhesive layer 56.

With the flow path forming substrate 10 on which the piezoelectricelements 300 are formed as described above, in other words, on the firstelectrodes 60, the adhesive layer 56, and the leading electrodes 90, aprotection substrate 30 that has the manifold unit 31 constituting atleast a part of a manifold 100 is bonded via an adhesive 35. Themanifold unit 31 is formed passing through of the protection substrate30 in the thickness direction thereof to the pressure generatingchambers 12 in the width direction thereof, and communicates with thecommunication unit 13 of the flow path forming substrate 10 describedabove, thereby constituting the manifold 100 that serves as a shared inkchamber of the pressure generating chambers 12 in the presentembodiment. In addition, by dividing the communication unit 13 of theflow path forming substrate 10 into a plural number for each pressuregenerating chamber 12, only the manifold unit 31 may set to be amanifold. Further, for example, it may be configured that only thepressure generating chambers 12 are provided in the flow path formingsubstrate 10, and the ink supply path 14 that communicates with themanifold 100 and the pressure generating chambers 12 may be provided fora member (for example, the elastic film 50, the adhesive layer 56, orthe like) that is interposed between the flow path forming substrate 10and the protection substrate 30.

In addition, in a region of the protection substrate 30 facing thepiezoelectric elements 300, a piezoelectric element holding unit 32 thathas a space large enough for not disrupting motions of the piezoelectricelements 300 is provided. The piezoelectric element holding unit 32preferably has a space large enough for not disrupting motions of thepiezoelectric elements 300, and the space may or may not be sealed.

As the protection substrate 30 described above, a material havingsubstantially the same thermal expansion coefficient as the flow pathforming substrate 10, for example, glass, a ceramic material, or thelike is preferably used, and in the present embodiment, the projectionsubstrate is formed using a silicon monocrystal substrate that is thesame material as the flow path forming substrate 10.

In addition, a through hole 33 passing through the protection substrate30 in the thickness direction is provided in the protection substrate30. In addition, a part of an end of the leading electrode 90 drawn fromeach of the piezoelectric elements 300 is provided so as to be exposedwithin the through hole 33.

In addition, a drive circuit 120 for driving the piezoelectric elements300 which are installed parallel to each other is fixed onto theprotection substrate 30. As the drive circuit 120, for example, acircuit board, a semiconductor integrated circuit (IC), or the like canbe used. In addition, the drive circuit 120 and the leading electrode 90are electrically connected to each other via connection wiring 121formed of conductive wires such as bonding wires.

In addition, a compliance substrate 40 that includes a sealing film 41and a fixing plate 42 is bonded with the protection substrate 30. Here,the sealing film 41 is formed of a flexible material having lowrigidity, and one face of the manifold unit 31 is sealed by the sealingfilm 41. In addition, the fixing plate 42 is formed of a relatively hardmaterial. Since a region of the fixing plate 42 facing the manifold 100forms an opening 43 which is completely removed in the thicknessdirection, one face of the manifold 100 is sealed only by the flexiblesealing film 41.

In an ink jet type recording head I of the present embodiment, ink istaken from an ink inlet connected to an external ink supply unit that isnot shown in the drawing, the inside from the manifold 100 to nozzleopenings 21 is filled with ink, then a voltage is applied to spacesbetween the first electrodes 60 and the second electrodes 80 each ofwhich is corresponding to the pressure generating chambers 12 accordingto a recording signal from the drive circuit 120, accordingly, theelastic film 50, the adhesive layer 56, the first electrodes 60, and thepiezoelectric layer 70 are deflected, which causes pressure inside eachof the pressure generating chambers 12 to increase, and consequently inkdrops are discharged from the nozzle openings 21.

Next, an example of a method for manufacturing the piezoelectric elementof the ink jet type recording head of the present embodiment will bedescribed.

First, a silicon dioxide film formed of silicon dioxide (SiO₂), or thelike constituting the elastic film 50 is formed on a surface of a wafer110 for a flow path forming substrate that is a silicon wafer usingthermal oxidation. Next, the adhesive layer 56 formed of titanium oxide,or the like is formed on the elastic film 50 (silicon dioxide film)using a reactive sputtering method, thermal oxidation, or the like.

Next, the first electrodes 60 are formed on the adhesive layer 56. To bespecific, the first electrodes 60 that is formed of platinum, indium,indium oxide, a staked structure thereof, or the like is formed on theadhesive layer 56. Note that the adhesive layer 56 and the firstelectrodes 60 can be formed using, for example, a sputtering method or avapor deposition method.

Next, the piezoelectric layer 70 is laminated on the first electrode 60.A manufacturing method of the piezoelectric layer 70 is not particularlylimited, but for example, the piezoelectric layer 70 can be formed usinga chemical solution method such as a Metal-Organic Decomposition (MOD)method or a gel-sol method in which a solution obtained by dissolving ordispersing an organic metal compound in a solvent is applied, dried, andthen burned at a high temperature, and thereby the piezoelectric layer70 formed of metal oxide is obtained. The piezoelectric layer 70 may beformed using other methods of a laser ablation method, the sputteringmethod, a pulsed laser deposition method (PLD method), a CVD method, anaerosol deposition method, or the like.

When the piezoelectric layer 70 is formed using, for example, a chemicalapplication method, 2-ethylhexanoate, acetate containing desiredelements are used as starting materials. For example, there are bismuth2-ethylhexanoate, barium 2-ethylhexanoate, iron 2-ethylhexanoate,titanium 2-ethylhexanate, and the like. A precursor solution is preparedby mixing n-octane solutions of the raw materials, and adjusting molarratios of metal elements so as to match with a stoichiometric ratio.Then, a piezoelectric film is formed using a spin coating method inwhich the precursor solution is dropped onto a bottom electrode that isproduced beforehand, rotated for 6 seconds at 500 rpm, and then asubstrate is rotated for 20 seconds at 3000 rpm. Next, the substrate isplaced on a hot plate, and dried for 2 minutes at 180° C. Next, thesubstrate is placed on the hot plate, and then degreasing is performedfor 2 minutes at 350° C. After repeating the process from solutionapplication to degreasing twice, the substrate is fired for 5 minutes at750° C. using an RTA device in an oxygen atmosphere. Then, the processis repeated five times, and thereby a piezoelectric layer 70 can beformed through a total of 10 times of application.

After the piezoelectric layer 70 is formed as described above, thesecond electrodes 80 formed of platinum, or the like is formed on thepiezoelectric layer 70 using the sputtering method, or the like, thepiezoelectric layer 70 and the second electrodes 80 are patterned at thesame time in a region facing each of the pressure generating chambers12, and thereby the piezoelectric elements 300 configured to have thefirst electrodes 60, the piezoelectric layer 70, and the secondelectrodes 80 are formed. Note that the patterning of the piezoelectriclayer 70 and the second electrode 80 can be collectively performed usingdry etching via a resist (not shown in the drawing) that is formed in apredetermined shape. Then, post annealing may be performed in atemperature range of 600° C. to 800° C. if necessary. Accordingly, afavorable interface between the piezoelectric layer 70 and the firstelectrodes 60 or the second electrodes 80 can be formed, and acrystalline property of the piezoelectric layer 70 can improve.

Next, over the entire face of the wafer for a flow path formingsubstrate, the leading electrodes 90 formed of, for example, gold (Au),or the like are formed, and then, the electrodes are patterned for eachof the piezoelectric elements 300 via, for example, a mask pattern thatincludes a resist, or the like.

Next, after a wafer for a protection substrate that is a silicon waferand will serve as a plurality of the protection substrates 30 is bondedwith the piezoelectric elements 300 of the wafer for a flow path formingsubstrate using the adhesive 35, the wafer for a flow path formingsubstrate is thinned so as to have a predetermined thickness.

Next, a mask film is newly formed on the wafer for the flow path formingsubstrate, and patterned in a predetermined shape.

Then, by performing anisotropic etching (wet etching) on the wafer for aflow path forming substrate using an alkali solution such as KOH via themask film, the pressure generating chambers 12, the communication unit13, the ink supply path 14, and the communication path 15 correspondingto the piezoelectric elements 300 are formed.

Then, unnecessary portions of outer circumferential parts of the waferfor a flow path forming substrate and the wafer for a protectionsubstrate are cut so as to be removed using, for example, dicing, or thelike. Then, after the mask film 52 of the face of the wafer for a flowpath forming substrate on the opposite side of the wafer for aprotection substrate is removed, the nozzle plate 20 through which thenozzle openings 21 are drilled is bonded with the wafer for a flow pathforming substrate, the compliance substrate 40 is bonded with the waferfor a protection substrate, and then by dividing the wafer for a flowpath forming substrate into one-chip-sized flow path forming substrate10, and the like as shown in FIG. 4, the ink jet type recording head Iof the present embodiment is formed.

Example 1

(Bi_(0.5), Na_(0.4), La_(0.1))TiO₃ was selected as the first component,NaNbO₃ was selected as the second component, and a piezoelectricmaterial having a composition in which the molar ratio of bothcomponents is 0.60:0.40 was formed as described below.

A precursor solution was prepared by mixing n-octane solutions ofbismuth 2-ethylhexanoate, sodium 2-ethylhexanoate, lanthanum2-ethylhexanoate, titanium 2-ethylhexanoate, and niobium2-ethylhexanoate as starting materials by adjusting the molar ratio ofthe metal elements so as to match with a stoichiometric ratio of thecomposition.

A piezoelectric film was formed using a spin coating method in which theprecursor solution was dropped onto a bottom electrode that had beenproduced beforehand, rotated for 6 seconds at 500 rpm, and then asubstrate was rotated for 20 seconds at 3000 rpm. Next, the substratewas placed on a hot plate and dried for 2 minutes at 180° C. Then, thesubstrate was placed on the hot plate to perform degreasing for 2minutes at 350° C. After repeating the process from solution applicationto degreasing twice, the substrate was burned for 5 minutes at 750° C.using an RTA device in an oxygen atmosphere. Then, the process wasrepeated five times, and thereby a piezoelectric layer was formedthrough a total of 10 times of application.

A head with the structure described above was configured usingpiezoelectric elements formed using the piezoelectric layer. d33 of thepiezoelectric element was 180 pC/N, and a Young's modulus thereof was 77GPa. Curie temperature Tc was 330° C. Thus, when a piezoelectricelement, particularly an actuator using the piezoelectric material isconfigured, it can be easily anticipated that significant displacementis obtained.

Example 2

(Bi_(0.5), Na_(0.4), La_(0.1))TiO₃ was selected as the first component,(K_(0.5), Na_(0.5))NbO₃ to which at least one element selected from Liand Ta had been added was selected as the second component, and apiezoelectric material having a composition in which the molar ratio ofboth components is 0.45:0.55 was formed as described below.

A precursor solution was prepared by mixing n-octane solutions ofbismuth 2-ethylhexanoate, sodium 2-ethylhexanoate, lanthanum2-ethylhexanoate, titanium 2-ethylhexanoate, potassium 2-ethylhexanoate,niobium 2-ethylhexanoate, lithium 2-ethylhexanoate, and tantalum2-ethylhexanoate as starting materials by adjusting the molar ratio ofthe metal elements so as to match with a stoichiometric ratio of thecomposition.

A piezoelectric film was formed using the spin coating method in whichthe precursor solution was dropped onto a bottom electrode that had beenproduced beforehand, rotated for 6 seconds at 500 rpm, and then asubstrate was rotated for 20 seconds at 3000 rpm. Next, the substratewas placed on a hot plate and dried for 2 minutes at 180° C. Then, thesubstrate was placed on the hot plate to perform degreasing for 2minutes at 350° C. After repeating the process from solution applicationto degreasing twice, the substrate was burned for 5 minutes at 750° C.using an RTA device in an oxygen atmosphere. Then, the process wasrepeated five times, and thereby a piezoelectric layer was formedthrough a total of 10 times of application.

A head with the structure described above was configured usingpiezoelectric elements formed using the piezoelectric layer. d33 of thepiezoelectric element was 220 pC/N, and a Young's modulus thereof was 70GPa. In addition, Curie temperature Tc4 was 330° C. Thus, when thepiezoelectric element, particularly an actuator using the piezoelectricmaterial is configured, it can be easily anticipated that significantdisplacement is obtained.

Example 3

(Bi_(0.5), Na_(0.4), La_(0.1))TiO₃ was selected as the first component,(Bi_(0.5), K_(0.5))TiO₃ was selected as the second component, and apiezoelectric material having a composition in which the molar ratio ofboth components is 0.33:0.67 was formed as described below.

A precursor solution was prepared by mixing n-octane solutions ofbismuth 2-ethylhexanoate, sodium 2-ethylhexanoate, lanthanum2-ethylhexanoate, titanium 2-ethylhexanoate, and potassium2-ethylhexanoate as starting materials by adjusting the molar ratio ofthe metal elements so as to match with a stoichiometric ratio of thecomposition.

A piezoelectric film was formed using the spin coating method in whichthe precursor solution was dropped onto a bottom electrode that had beenproduced beforehand, rotated for 6 seconds at 500 rpm, and then asubstrate was rotated for 20 seconds at 3000 rpm. Next, the substratewas placed on a hot plate and dried for 2 minutes at 180° C. Then, thesubstrate was placed on the hot plate to perform degreasing for 2minutes at 350° C. After repeating the process from solution applicationto degreasing twice, the substrate was burned for 5 minutes at 750° C.using an RTA device in an oxygen atmosphere. Then, the process wasrepeated five times, and thereby a piezoelectric layer was formedthrough a total of 10 times of application.

A head with the structure described above was configured usingpiezoelectric elements formed using the piezoelectric layer. d33 of thepiezoelectric element was 270 pC/N, and a Young's modulus thereof was 75GPa. In addition, Curie temperature Tc4 was 347° C. Thus, when thepiezoelectric element, particularly an actuator using the piezoelectricmaterial is configured, it can be easily anticipated that significantdisplacement is obtained.

Example 4 and Other Embodiment

(Bi_(0.5), Na_(0.4), Ba_(0.1))TiO₃, and (Bi_(0.5), Na_(0.5)) TiO₃,(Bi_(0.5), Na_(0.5))TiO₃ to which Ca is added, (Bi_(0.7),La_(0.3))(Sc_(0.1), Ti_(0.9))O₃, and (Bi_(0.7), La_(0.3))(Zn_(0.2),Ti_(0.8))O₃ were selected as the first component and NaNbO₃ to which atleast one element selected from Li and Ta was selected as the secondcomponent, and then a piezoelectric material was formed as follows. Themolar ratio of the first components and the second components wasdecided based on an MPB that is defined at a point at which dependencyof a dielectric constant on a composition ratio becomes the maximum anda point at which a Young's modulus becomes the minimum.

As a starting material, 2-ethylhexanoate was employed. An n-octanesolution was employed as a solvent, they were mixed by adjusting themolar ratio of the metal elements so as to match with a stoichiometricratio of the composition, and accordingly, a precursor solution wasprepared.

An MPB is not always formed only in a combination of a rhombohedralcrystal and a tetragonal crystal. Although there are differences in theeffect of the MPB, there are the following combination cases.

I Tetragonal system and orthorhombic system

II Tetragonal system and monoclinic system

III Orthorhombic system and monoclinic system

Table 1 describes compositions (A site and B site) composing aperovskite-type crystal (ABO₃ wherein A and B are metal elements),crystal systems, and Curie temperature Tc thereof. The elements can bearbitrarily selected so that a combination of crystal systems differentfrom Table 1 can be realized. In this case, Tc1 and Tc2, can be selectedby adjusting an additive and an amount of addition. As elementsappropriate for the additive, elements other than the elements describedin Table 1 are exemplified below:

Mn, Ge, Si, B, Cu, and Ag.

TABLE 1 Composition, Tc, and Crystal System CRYSTAL SYSTEM (AT ROOM ASITE B SITE Tc ADDITIVE TEMPERATURE) Ag Nb 67 M Bi NiTi 225 M Ba HfTi 25R Ba SnTi 50 R Ba ZrTi 70 R NaBi Ti 200 R BiNa Ti 268 Sr R BiNa Ti 268Ca R BiNaBa Ti 280 R BiNa Ti 320 R BiNa Ti 200~350 Li, La R BiLa ZnTi350 R BiNa ScTi 358 R Ag Ta 370 R Ba Bi 370 R Bi MgTi 395 R Si Sc 400 RBi Sc 480 R Bi Fe 850 R BiNaLa Ti 335-370 R K Nb 200~435 Sr, Li, Sb, TaO KNa Nb 200~435 Sr, Li, Sb, Ta O Na Nb 365 O Na Ta 480 O Cd Hf 600 O SrZr 700 O Ca Ti 1260 O BaCa Ti 70 T Ba Ti 123 T Na Nb 360 T BiK Ti 380 TT: Tetragonal system R: Rhombohedral system M: Monoclinic system O:Orthorhombic system Other Embodiment

Hereinabove, embodiments of the invention have been described, but abasic configuration of the invention is not limited to ones describedabove. Although, for example, a silicon monocrystal substrate isexemplified as the flow path forming substrate 10 in the embodimentdescribed above, the configuration is not particularly limited thereto,and a material, for example, an SOI substrate, glass, or the like may beused.

Further, in the embodiment described above, although the piezoelectricelements 300 obtained by laminating the first electrodes 60, thepiezoelectric layer 70, and the second electrodes 80 on a substrate (theflow path forming substrate 10) in order are exemplified, they are notparticularly limited thereto, and the invention can also be applied to alongitudinal oscillation type piezoelectric element in whichpiezoelectric materials and electrode forming materials are laminated inan alternate manner and extend in an axial direction.

The piezoelectric layer may not be a thin film as described above, butmay be a bulk member. When the layer is formed as a bulk member,carbonate or oxide is used as a starting material. Examples are K₂CO₃,Na₂CO₃, Nb₂O₅, and the like. The starting materials are measured so asto match with a stoichiometric ratio and then wet-blended with ethanolusing a ball mill. After the obtained mixture is dried, it is calcinedfor 3 hours at 700° C. The calcined powder is pulverized and mixed usingmortar with addition of an appropriate amount of PVA as a binder, and iscaused to pass through a sieve of 150 mesh to adjust granularitythereof, and then the obtained powder is formed into a discoid palletusing a single-axis press device. Next, the formed pallet and residualcalcined powder are put into a melting pot and burned for 3 hours at1100° C., thereby obtaining a discoid oxide. Then, both faces of theobtained discoid oxide are polished so as to have surfaces, are coatedwith silver paste and burned, and accordingly, a piezoelectric bodyprovided with silver electrodes can be obtained. Note that, in themanufacturing of the piezoelectric body in bulk, barium carbonate,titanium oxide, bismuth oxide, tin oxide, iron oxide, zirconium oxide,lanthanum oxide, lithium carbonate, and the like can be exemplified asstarting materials.

In addition, the ink jet type recording head of the embodimentconstitutes a part of a recording head unit that includes an ink flowpath that communicates with an ink cartridge, or the like, and ismounted in an ink jet type recording apparatus. FIG. 7 is a schematicdiagram illustrating an example of such an ink jet type recordingapparatus.

As illustrated in FIG. 7, recording head units 1A and 1B that have theink jet type recording head I are provided so as to enable cartridges 2Aand 2B constituting an ink supply unit to attach to and detach from theunits, and a carriage 3 on which the recording head units 1A and 1B aremounted is provided so as to freely move on a carriage shaft 5 installedin the main body 4 of the apparatus in the axial direction. Therecording head units 1A and 1B are respectively set to discharge, forexample, a black ink composition and a color ink composition.

In addition, drive force of a drive motor 6 is transmitted to thecarriage 3 via a plurality of gear wheels, which are not shown in thedrawing, and a timing belt 7, and accordingly, the carriage 3 on whichthe recording head units 1A and 1B are mounted is moved along thecarriage shaft 5. On the other hand, the main body 4 of the apparatus isprovided with a platen 8 along the carriage shaft 5, and a recordingsheet S that is a recording medium such as paper fed by a feedingroller, or the like, which is not shown in the drawing, is designed tobe wounded around the platen 8 and then transported.

In the example illustrated in FIG. 7, although the ink jet typerecording head units 1A and 1B are set to respectively have one ink jettype recording head I, they are not particularly limited thereto, andfor example, either of the ink jet type recording head units 1A or 1Bmay have two or more ink jet type recording heads.

Note that, in the embodiment described above, the ink jet type recordinghead is exemplified as an example of a liquid ejecting head, however,the invention widely targets liquid ejecting heads in general, and canof course be applied to liquid ejecting heads that eject liquid otherthan ink. As other liquid ejecting heads, for example, various recordingheads used in image recording apparatuses such as printers, colormaterial ejecting heads used in manufacturing of color filters of liquidcrystal displays, electrode material ejecting heads used in formation ofelectrodes of organic EL displays, field emission displays (FED),bioorganic substance ejecting heads used in manufacturing of bio chips,and the like can be exemplified.

Ultrasonic Sensor and Piezoelectric Motor

Since the above piezoelectric element exhibits a satisfactory insulatingproperty and piezoelectric characteristic, it can be applied to apiezoelectric element of a liquid ejecting head represented by an inkjet-type recording head as described above, however, it is not limitedthereto. Since the above piezoelectric element exhibits an excellentdisplacement characteristic, it is not limited to the liquid ejectinghead represented by an ink jet-type recording head, it can beappropriately used by being mounted on liquid ejecting apparatuses,ultrasonic sensors, piezoelectric motors, ultrasonic motors,piezoelectric transformers, oscillation-type dust removal apparatuses,pressure-electric converters, ultrasonic wave transmitting machines,pressure sensors, acceleration sensors, or the like.

Power Generator

In addition, since the piezoelectric element exhibits a satisfactoryenergy-electric conversion capability, it can be appropriately used bybeing mounted on a power generator. Examples of the power generatorinclude a power generator using a pressure-electric conversion effect, apower generator using an electronic excitation (photovoltaic power) bylight, a power generator using an electronic excitation (thermo-electricforce) by heat, and a power generator using oscillating.

Note that, the piezoelectric element can be appropriately used inpyroelectric device such as infrared detectors, terahertz detectors,temperature sensors, and thermo-sensitive sensors or ferroelectricelements such as a ferroelectric memory.

The entire disclosures of Japanese Patent Application Nos. 2013-137281filed Jun. 28, 2013 and 2014-001902 filed Jan. 8, 2014 are expresslyincorporated by reference herein.

What is claimed is:
 1. A piezoelectric material containing: a firstcomponent that is a rhombohedral crystal that has a complex oxide with aperovskite structure and Curie temperature Tc1; and a second componentthat is a crystal other than a rhombohedral crystal has a complex oxidewith the perovskite structure and Curie temperature Tc2, wherein anabsolute value of a difference between Tc1 and Tc2 is equal to or lessthan 50° C.
 2. The piezoelectric material according to claim 1, whereina composition near an MPB line is provided in a phase diagram thatemploys a composition ratio of the first component to the secondcomponent for a horizontal axis and temperature for a vertical axis. 3.The piezoelectric material according to claim 1, wherein|Tc1−Tc2|/|Tc1+Tc2|≦0.1.
 4. The piezoelectric material according toclaim 1, wherein a Curie temperature of the material is equal to orhigher than 280° C.
 5. The piezoelectric material according to claim 1,wherein a molar ratio of the first component to (the first component+thesecond component) is 0.1 to 0.9.
 6. The piezoelectric material accordingto claim 1, wherein the first component is (Bi, Na, La)TiO₃, and thesecond component is NaNbO₃.
 7. The piezoelectric material according toclaim 1, wherein the first component is (Bi, Na, La)TiO₃, and the secondcomponent is (K, Na)NbO₃ to which at least one of Li and Ta is added. 8.The piezoelectric material according to claim 1, wherein the firstcomponent is (Bi, Na, La)TiO₃, and the second component is (Bi, K)TiO₃.9. The piezoelectric material according to claim 1, wherein the firstcomponent is one of (Bi, Na, Ba)TiO₃, (Bi, Na)TiO₃, and (Bi, Na)TiO₃ towhich Ca is added, (Bi, La) (Sc, Ti)O₃, and (Bi, La) (Zn, Ti)O₃, and thesecond component is NaNbO₃ to which at least one of Li and Ta is added.10. A piezoelectric element comprising: a piezoelectric layer formed ofthe piezoelectric material according to claim 1; and an electrodeprovided on the piezoelectric layer.
 11. A piezoelectric elementcomprising: a piezoelectric layer formed of the piezoelectric materialaccording to claim 2; and an electrode provided on the piezoelectriclayer.
 12. A piezoelectric element comprising: a piezoelectric layerformed of the piezoelectric material according to claim 3; and anelectrode provided on the piezoelectric layer.
 13. A piezoelectricelement comprising: a piezoelectric layer formed of the piezoelectricmaterial according to claim 4; and an electrode provided on thepiezoelectric layer.
 14. A piezoelectric element comprising: apiezoelectric layer formed of the piezoelectric material according toclaim 5; and an electrode provided on the piezoelectric layer.
 15. Apiezoelectric element comprising: a piezoelectric layer formed of thepiezoelectric material according to claim 6; and an electrode providedon the piezoelectric layer.
 16. A liquid ejecting head comprising: apressure generating chamber that communicates with a nozzle opening; anda piezoelectric element that has a piezoelectric layer and an electrodeprovided on the piezoelectric layer, wherein the piezoelectric layer isformed of the piezoelectric material according to claim
 1. 17. A liquidejecting apparatus comprising: the liquid ejecting head according toclaim
 16. 18. An ultrasonic sensor comprising: a vibrating unit thattransmits a displacement which is caused due to driving of thepiezoelectric element according to claim 10 to the outside; and amatching layer that transmits a generated pressure wave to the outside.19. A piezoelectric motor comprising: at least a vibrator in which thepiezoelectric element according to claim 10 is arranged, and a movingbody contacting the vibrator.
 20. A power generator comprising: anelectrode taking out a charge generated by the piezoelectric elementaccording to claim 10.